1. Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315201, China 2. Key Laboratory of Marine Materials and Related Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
Cite this article:
Wentao LI,Zhenyu WANG,Dong ZHANG,Jianguo PAN,Peiling KE,Aiying WANG. Preparation of Ti2AlC Coating by the Combination of a Hybrid Cathode Arc/Magnetron Sputtering with Post-Annealing. Acta Metall Sin, 2019, 55(5): 647-656.
Nuclear power generation provides a reliable and economic supply of electricity, due to low carbon emissions and relatively few waste. However, the reaction between zirconium and steam at high temperature is accompanied by the release of large amounts of hydrogen gas, which will bring serious consequences. After the Fukushima nuclear accident, the concept of accident-tolerant fuels (ATF) has been proposed and widely investigated. In terms of nuclear claddings, one key requirement is reduced oxidation kinetics with high-temperature steam and hence significantly reduced heat and hydrogen generation. An economical and simple method could be the preparation of protective coatings on the surface of zirconium alloys to improve the oxidation resistance. The MAX phase has been considered to be one of the most promising coating materials for nuclear cladding coatings. In this work, Ti-Al-C coatings with different Ti/Al ratios have been deposited on Zirlo alloy using a hybrid arc/magnetron sputtering method, and the Ti2AlC coatings were obtained by post-annealing. The effects of Ti/Al ratios and annealing temperatures on the phase and microstructure of Ti-Al-C coatings after annealing were studied by SEM, EDS, XRD, Raman spectrometer and TEM. It is found that Ti-Al-C coatings with different Ti/Al ratios deposited by the hybrid cathode arc/magnetron sputtering are a multi-layer structure of an alternative Al-rich layer and TiCx layer. The as-deposited coatings are compact with a small amount of large particles. The Ti/Al ratio has an important influence on the phase structure of the annealed coating. When the Ti/Al ratio is 2.04, the highest purity and crystallinity of Ti2AlC are obtained. TiC and Ti3AlC impurities will form within the coating at a higher Ti/Al ratio (3.06), while the purity and crystallinity of Ti2AlC will decrease at a lower Ti/Al ratio (0.54). In addition, the annealing temperature affects the formation of Ti2AlC to a great extent. When the Ti/Al ratio is 2.38, the optimum temperature for Ti-Al-C coatings to Ti2AlC coatings is at 750 ℃. The atom cannot diffuse fully at a lower annealing temperature (600 ℃), which is difficult to form the Ti2AlC phase, while a higher annealing temperature (900 ℃) will enable the formation of Ti2AlC coatings with more TiC, TiAlx and other impurities.
Fund: National Science and Technology Major Project of China(2015ZX06004-001);China Postdoctoral Science Foundation(2018M632513);Natural Science Foundation of Zhejiang Province(LQ19E01002);Ningbo Municipal Key Technologies Research and Development Program(2017B10042)
Fig.1 Schematic of the hybrid cathodic arc/magnetron sputter (No.1~No.5 samples were suspended from top to bottom on a rotating sample holder in the chamber)
Procedure
Ar flow
mL·min-1
CH4 flow
mL·min-1
Presure
Pa
Bias voltage
V
Current / A
Ion gun
Arc
Sputter
Etching
40
-
-
-300
0.2
-
-
TiC layer
200
50
3.99
-100
-
70
-
Ti-Al-C layer
200
15
3.99
-200
-
60
8.0
Table 1 Deposition parameters of Ti-Al-C coatings
Sample
No.1
No.2
No.3
No.4
No.5
As-deposited
2.38
2.04
1.64
0.66
0.42
As-annealed
3.06
1.75
1.09
0.99
0.54
Table 2 Ti/Al ratios of No.1~No.5 coatings in as-deposited and annealed samples
Fig.2 Surface SEM images of No.1 (a), No.2 (b), No.3 (c), No.4 (d) and No.5 (e) coatings in as-deposited samples
Fig.3 Surface SEM images of No.1 (a), No.2 (b), No.3 (c), No.4 (d) and No.5 (e) coatings annealed at 800 ℃ for 1 h
Fig.4 Cross-sectional SEM images of No.1 (a), No.2 (b), No.3 (c), No.4 (d) and No.5 (e) coatings annealed at 800 ℃ for 1 h
Fig.5 EDS line-scanning and element mapping results of No.2 (a) and No.4 (b) samples annealed at 800 ℃ for 1 h
Fig.6 XRD spectra of the No.1~No.5 samples annealed at 800 ℃ for 1 h
Fig.7 Raman spectra of the as-deposited No.1 sample and the annealed one (E1g, E2g and A1g stand for three Raman active modes in MAX phase, respectively)
Fig.8 HRTEM images of as-deposited (a~c) and annealed (d, e) No.1 coatings, and fast Fourier transform image of area A in Fig.8e (f) (Illustration in Fig.8a shows selected-area electron diffraction pattern of as-deposited coating, and inset in Fig.8b shows line scan pattern of the coating surface under TEM, corresponding to the line)
Fig.9 Surface SEM images of No.1 sample as-deposited (a) and annealed at 600 ℃ (b), 650 ℃ (c), 700 ℃ (d), 750 ℃ (e), 800 ℃ (f), 850 ℃ (g) and 900 ℃ (h) for 1 h
Fig.10 Cross-section SEM images and EDS line-scanning results of No.1 sample as-deposited (a) and annealed at 600 ℃ (b), 650 ℃ (c), 700 ℃ (d), 750 ℃ (e), 800 ℃ (f), 850 ℃ (g) and 900 ℃ (h) for 1 h
Fig.11 XRD spectra of the No.1 sample annealed at 600~900 ℃ for 1 h
Fig.12 Raman spectra of the No.1 samples annealed at 600~900 ℃ for 1 h
Fig.13 Changes of grain size at (0002) and (10$\bar{1}$3) plane with different annealing temperatures for No.1 sample
[1]
BarsoumM W. The MN+1AXN phases: A new class of solids: Thermodynamically stable nanolaminates[J]. Prog. Solid State Chem., 2000, 28: 201
[2]
EklundP, BeckersM, JanssonU, et al. The Mn+1AXn phases: Materials science and thin-film processing[J]. Thin Solid Films, 2010, 518: 1851
[3]
YangH Y, ZhangR Q, PengX M, et al. Research progress regarding surface coating of zirconium alloy cladding[J].Surf. Technol., 2017, 46(1): 69
YuehK, TerraniK A. Silicon carbide composite for light water reactor fuel assembly applications[J]. J. Nucl. Mater., 2014, 448: 380
[5]
TerraniK A, ZinkleS J, SneadL L. Advanced oxidation-resistant iron-based alloys for LWR fuel cladding[J]. J. Nucl. Mater., 2014, 448: 420
[6]
LuoK, ZhaX H, HuangQ, et al. Theoretical investigations on helium trapping in the Zr/Ti2AlC interface[J]. Surf. Coat. Technol., 2017, 322: 19
[7]
BasuS, ObandoN, GowdyA, et al. Long-term oxidation of Ti2AlC in air and water vapor at 1000-1300 ℃ temperature range[J]. J. Electrochem. Soc., 2012, 159: C90
[8]
LiS B, SongG M, KwakernaakK, et al. Multiple crack healing of a Ti2AlC ceramic[J]. J. Eur. Ceram. Soc., 2012, 32: 1813
[9]
MaierB R, Garcia-DiazB L, HauchB, et al. Cold spray deposition of Ti2AlC coatings for improved nuclear fuel cladding[J]. J. Nucl. Mater., 2015, 466: 712
[10]
FrodeliusJ, EklundP, BeckersM, et al. Sputter deposition from a Ti2AlC target: Process characterization and conditions for growth of Ti2AlC[J]. Thin Solid Films, 2010, 518: 1621
[11]
FengZ J, KeP L, WangA Y. Preparation of Ti2AlC MAX phase coating by DC magnetron sputtering deposition and vacuum heat treatment[J]. J. Mater. Sci. Technol., 2015, 31: 1193
[12]
FengZ J, KeP L, HuangQ, et al. The scaling behavior and mechanism of Ti2AlC MAX phase coatings in air and pure water vapor[J]. Surf. Coat. Technol., 2015, 272: 380
[13]
FuJ J, ZhangT F, XiaQ X, et al. Oxidation and corrosion behavior of nanolaminated MAX-phase Ti2AlC film synthesized by high-power impulse magnetron sputtering and annealing[J]. J. Nanomater., 2015, 2015: 213128
[14]
YeomH, HauchB, CaoG P, et al. Laser surface annealing and characterization of Ti2AlC plasma vapor deposition coating on zirconium-alloy substrate[J]. Thin Solid Films, 2016, 615: 202
[15]
TangC, KlimenkovM, JaentschU, et al. Synthesis and characterization of Ti2AlC coatings by magnetron sputtering from three elemental targets and ex-situ annealing[J]. Surf. Coat. Technol., 2017, 309: 445
[16]
GuenetteM C, TuckerM D, IonescuM, et al. Cathodic arc co-deposition of highly oriented hexagonal Ti and Ti2AlC MAX phase thin film[J]. Thin Solid Films, 2010, 519: 766
[17]
RosénJ, RyvesL, O ?PerssonP , et al. Deposition of epitaxial Ti2AlC thin films by pulsed cathodic arc[J]. J. Appl. Phys., 2007, 101: 056101
[18]
ShuR, GeF F, MengF P, et al. One-step synthesis of polycrystalline V2AlC thin films on amorphous substrates by magnetron co-sputtering[J]. Vacuum, 2017, 146: 106
[19]
WangJ Y, ZhouY C, LiaoT, et al. A first-principles investigation of the phase stability of Ti2AlC with Al vacancies[J]. Scr. Mater., 2008, 58: 227
[20]
LiJ J, HuL F, LiF Z, et al. Variation of microstructure and composition of the Cr2AlC coating prepared by sputtering at 370 ℃ and 500 ℃[J]. Surf. Coat. Technol., 2010, 204: 3838
[21]
SuR R, ZhangH L, O'ConnorD J, et al. Deposition and characterization of Ti2AlC MAX phase and Ti3AlC thin films by magnetron sputtering[J]. Mater. Lett., 2016, 179: 194
[22]
LiuJ Z, ZuoX, WangZ Y, et al. Fabrication and mechanical properties of high purity of Cr2Al Ccoatings by adjustable Al contents[J]. J. Alloys Compd., 2018, 753: 11
[23]
LiY M, ZhaoG R, QianY H, et al. Deposition and characterization of phase-pure Ti2AlC and Ti3AlC2 coatings by DC magnetron sputtering with cost-effective targets[J]. Vacuum, 2018, 153: 62
[24]
WangZ Y, LiuJ Z, WangL, et al. Dense and high-stability Ti2AlN MAX phase coatings prepared by the combined cathodic arc/sputter technique[J]. Appl. Surf. Sci., 2017, 396: 1435
[25]
LowI M, PangW K, KennedyS J, et al. High-temperature thermal stability of Ti2AlN and Ti4AlN3: A comparative diffraction study[J]. J. Eur. Ceram. Soc., 2011, 31: 159
[26]
WilhelmssonO, PalmquistJ P, NybergT, et al. Deposition of Ti2AlC and Ti3AlC2 epitaxial films by magnetron sputtering[J]. Appl. Phys. Lett., 2004, 85: 1066
[27]
LiJ J, QianY H, NiuD, et al. Phase formation and microstructure evolution of arc ion deposited Cr2AlC coating after heat treatment[J]. Appl. Surf. Sci., 2012, 263: 457
[28]
MiernikK, WalkowiczJ. Spatial distribution of microdroplets generated in the cathode spots of vacuum arcs[J]. Surf. Coat. Technol., 2000, 125: 161
[29]
BandyopadhyayD, SharmaR C, ChakrabortiN. The Ti-Al-C system (titanium-aluminum-carbon)[J]. J. Phase Equilib., 2000, 21: 195
[30]
PresserV, NaguibM, ChaputL, et al. First-order Raman scattering of the MAX phases: Ti2AlN, Ti2AlC0.5N0.5, Ti2AlC, (Ti0.5V0.5)2AlC, V2AlC, Ti3AlC2, and Ti3GeC2[J]. J. Raman Spectro., 2012, 43: 168
[31]
HakamadaM, NakamotoY, MatsumotoH, et al. Relationship between hardness and grain size in electrodeposited copper films[J]. Mater. Sci. Eng., 2007, A457: 120
[32]
TangC C, SteinbrueckM, StueberM, et al. Deposition, characterization and high-temperature steam oxidation behavior of single-phase Ti2AlC-coated Zircaloy-4[J]. Corros. Sci., 2018, 135: 87
[33]
WangJ M, WangJ Y, ZhouY C. Stable M2AlC (0001) surfaces (M=Ti, V and Cr) by first-principles investigation[J]. J. Phys. Condens Matter, 2008, 20: 225006
